The present invention relates to a polyester film for dry film resists. More specifically, it relates to a polyester film for dry film resists, which is excellent in terms of transparency, slipperiness, winding properties, separation work efficiency and resolution.
In recent years, a dry film resist (may be abbreviated as DFR hereinafter) method has been used to produce a printed wiring circuit board. A photoresist laminate used in this DFR method is generally a laminate structure comprising a base layer, a photoresist layer and a protective layer laminated in the mentioned order and a polyester film having excellent mechanical, chemical and optical properties has been used as the base layer.
The DFR method comprises removing the protective layer of the photoresist laminate having the above structure, joining the exposed photoresist layer to a conductive matrix mounted on a substrate and joining a glass sheet printed with an electronic circuit to the photoresist film base layer. Thereafter, the resulting laminate was exposed to ultraviolet radiation having a wavelength around 365 nm from the glass sheet side to exposure and cure a photosensitive resin constituting the photoresist layer, the glass sheet and the base layer are removed, and an uncured portion of the photoresist layer is removed by a solvent or the like. Further, when etching is carried out with an acid, the exposed conductive matrix dissolves, the photoresist resin reacts, and an unremoved portion of the conductive matrix remains as it is. When the remaining photoresist layer is then removed by suitable means, the conductive matrix layer is formed on the substrate as a circuit.
A polyester film used as the base layer in the above DFR method is required to have high transmission of light having a wavelength around 365 nm and a low haze value. When the photoresist layer is to be exposed, as light passes through the base layer, if the transmission of the base layer is low, the photoresist layer may not be exposed fully or light may be scattered with the result of poor resolution.
In recent years, portable telephones, PHS and personal computers have been in growing demand and the improvement of productivity of photoresist films for the production of electronic circuits for use in these devices has been required.
To improve handling ease for the production of photoresist films or the handling ease of a photoresist film, the polyester film of the base layer is required to have moderate slipperiness, winding properties and tear strength. The method of forming fine protrusions on the surface of a polyester film by containing fine particles in the film has been used to achieve the above properties. JP-A 7-333853 (the term xe2x80x9cJP-Axe2x80x9d as used herein means an xe2x80x9cunexamined published Japanese patent applicationxe2x80x9d) proposes a biaxially oriented laminated polyester film for photoresists in which the outermost layer on at least one side contains particles (globular or amorphous silica particles, globular crosslinked polymer particles, etc.) having an average particle diameter of 0.01 to 3.0 xcexcm and has a surface roughness Ra (center line average roughness) of 0.005 xcexcm or more, an Rt (maximum height) of less than 1.5 xcexcm and a film haze of 1.5% or less.
However, this polyester film may be unsatisfactory in terms of transmission of light having a wavelength around 365 nm with the result of reduced resolution, thereby making it difficult to obtain a fine circuit pattern. Further, the above laminated polyester film has a problem such as high production cost.
As the recent enactment of a home electric appliance recycling law promotes the recycling of electric products and products for producing the same, materials constituting these are required to contain no antimony, tin or lead. Antimony compounds have been used as a polycondensation catalyst for producing a polyester polymer for forming a polyester film. Use of polycondensation catalysts other than these antimony compounds is now desired.
It is an object of the present invention to provide a polyester film for dry film resists, which solves the above problems of the prior art and meets requirements for the transmission of light, especially light having a wavelength around 365 nm, slipperiness, winding properties and resolution.
It is another object of the present invention to provide a polyester film for dry film resists, which further has excellent recyclability in addition to the above properties.
It is still another object of the present invention to provide a laminated polyester film for dry film resists, which prevents reflection and has excellent fine pattern circuit formability in addition to the above properties.
It is a further object of the present invention to provide a dry film resist comprising the above polyester film of the present invention as a base film.
Other objects and advantages of the present invention will become apparent from the following description.
According to the present invention, firstly, the above objects and advantages of the present invention are attained by a biaxially oriented polyester film for dry film resists, which comprises (1) an aromatic polyester containing metals derived from a polycondensation catalyst in a total amount of less than 150 ppm and metal antimony out of the above metals in an amount of 15 mmol % or less based on the total of all the acid components and which has (2) a haze value of 3% or less, (3) a transmission of ultraviolet radiation having a wavelength of 365 nm of 86% or more and (4) a thickness of 10 to 25 xcexcm.
According to the present invention, secondly, the above objects and advantages of the present invention are attained by a laminated polyester film which comprises (1) the above biaxially oriented polyester film of the present invention and a lubricating layer formed on at least one side of the polyester film and which has (2) a haze value of 3% or less and (3) a transmittance of ultraviolet radiation having a wavelength of 365 nm of 86% or more.
According to the present invention, thirdly, the above objects and advantages of the present invention are attained by a dry film resist comprising the biaxially oriented polyester film or laminated polyester film of the present invention, a photoresist layer and a protective film layer laminated in the mentioned order.
The present invention will be described in detail hereinbelow. A description is first given of the biaxially oriented polyester film of the present invention.
The aromatic polyester constituting the film of the present invention is preferably a polyethylene terephthalate homopolymer or a copolymer comprising ethylene terephthalate as the main recurring unit. The polyethylene terephthalate homopolymer is suitably used in a DFR film because it has high mechanical strength and a high transmission of short-wavelength visible radiation and near ultraviolet radiation close to that radiation.
In the present invention, the comonomer of the copolyester may be a dicarboxylic acid component or diol component. Examples of the dicarboxylic acid component include aromatic dicarboxylic acids such as isophthalic acid and phthalic acid; aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and decanedicarboxylic acid; and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. Examples of the diol component include aliphatic diols such as 1,4-butanediol, 1,6-hexanediol and diethylene glycol; alicyclic diols such as 1,4-cyclohexanedimethanol; and aromatic diols such as bisphenol A. They may be used alone or in combination of two or more. Out of these, isophthalic acid is particularly preferred because it gives a copolymer having high transparency and tear strength.
The amount of the comonomer which depends on its type is such that the melting point of the obtained polymer should be 245 to 258xc2x0 C. (melting point of the homopolymer). When the melting point is lower than 245xc2x0 C., heat resistance deteriorates, heat shrinkage becomes large and film flatness lowers.
The melting point of the polyester is measured by obtaining a melting peak at a temperature elevation rate of 20xc2x0 C./min using the 910 DSC of Du Pont Instruments Co., Ltd. The amount of the sample is about 20 mg.
The intrinsic viscosity (orthochlorophenol, 35xc2x0 C.) of the polyester is preferably 0.52 to 1.50, more preferably 0.57 to 1.00, particularly preferably 0.60 to 0.80. When the intrinsic viscosity is lower than 0.52, the tear strength may be insufficient disadvantageously. When the intrinsic viscosity is higher than 1.50, productivity in the raw material production step and the film formation step may be impaired.
The aromatic polyester such as polyethylene terephthalate or copolyester in the present invention is not limited by its production process. For instance, in the case of terephthalic acid, ethylene glycol and copolyester, a comonomer is further added to carry out an esterification reaction and then the obtained reaction product is polycondensed until a targeted polymerization degree is achieved to produce polyethylene terephthalate or copolyethylene terephthalate; or in the case of dimethyl terephthalate, ethylene glycol and copolyester, a comonomer is added to carry out an ester exchange reaction and then the obtained reaction product is polycondensed until a targeted polymerization degree is achieved to produce polyethylene terephthalate or copolyethylene terephthalate. Polyethylene terephthalate or copolyethylene terephthalate obtained by the above method (melt polymerization) may be further polymerized in a solid state (solid-phase polymerization) as required to produce a polymer having a higher degree of polymerization.
The catalyst used for the above polycondensation reaction is preferably a combination of a titanium compound (Ti compound), germanium compound (Ge compound), manganese compound (Mn compound) and antimony compound (Sb compound), or a magnesium compound (Mg compound). These catalysts may be used alone or in combination. Out of these, a germanium compound and a titanium compound are preferred and a germanium compound is particularly preferred.
Preferred examples of the titanium compound include titanium tetrabutoxide and titanium acetate. Preferred examples of the germanium compound include (a) amorphous germanium oxide, (b) fine crystalline germanium oxide, (c) a solution of germanium oxide dissolved in glycol in the presence of an alkali metal, alkali earth metal or compound thereof and (d) an aqueous solution of germanium oxide. Further, when 10 mmol % or less of an antimony compound and/or a titanium compound are/is used, resolution can be improved and production cost can be reduced advantageously.
The total content of the residual polycondensation metal catalysts in the aromatic polyester is less than 150 ppm, preferably 30 to 120 ppm, more preferably 50 to 100 ppm based on weight. Out of these, the content of metal antimony is 15 mmol % or less, preferably 10 mmol % or less, more preferably 5 mmol % or less, particularly preferably 0 mmol % based on 1 mol of the total of all the acid components.
When the total content of the residual polycondensation metal catalysts in the aromatic polyester is higher than 150 ppm, the transmittance of radiation having a wavelength around 365 nm may become less than 86% based on a film thickness of 16 xcexcm disadvantageously. To reduce the total content of the residual polycondensation metal catalysts in the aromatic polyester to 150 ppm or less, use of an antimony-based catalyst must be avoided, which is preferred from the viewpoint of the home electric appliance recycling law.
The above aromatic polyester may be optionally mixed with additives such as an antioxidant, thermal stabilizer, viscosity modifier, plasticizer, color improving agent, lubricant and nucleating agent.
Out of these, lubricant fine particles are added as the lubricant to secure the work efficiency (slipperiness) of the film. Any lubricant fine particles may be used. Inorganic lubricants include silica, alumina, titanium dioxide, calcium carbonate and barium sulfate. Organic lubricants include silicone resin particles and crosslinked polystyrene particles. Out of these, porous silica particles which are agglomerates of primary particles are particularly preferred. The porous silica particles have a characteristic property to improve the transparency of the film because voids are hardly produced around the particles when the film is stretched.
The average particle diameter of the primary particles constituting the porous silica particles is preferably in the range of 0.001 to 0.1 xcexcm. When the average particle diameter of the primary particles is smaller than 0.001 xcexcm, extremely fine particles produced by the cracking of a slurry agglomerate, causing a reduction in transparency. When the A, average particle diameter of the primary particles is larger than 0.1 xcexcm, the porosity of the particles is lost with the result that the feature that voids are hardly produced may be lost. Further, the pore volume of the agglomerated particle is preferably 0.5 to 2.0 ml/g, more preferably 0.6 to 1.8 ml/g. When the pore volume is smaller than 0.5 ml/g, the porosity of the particles is lost, voids may be produced and transparency may be lowered disadvantageously. When the pore volume is larger than 2.0 ml/g, cracking and agglomeration easily occur, thereby making it difficult to control the diameter of the particle. The average particle diameter of the above porous silica particles is preferably in the range of 0.05 xcexcm or more and less than 3.0 xcexcm, more preferably 0.1 xcexcm to 2.5 xcexcm. The amount of the porous silica particles is preferably 50 ppm or more and less than 1,000 ppm, more preferably 100 ppm to 800 ppm. When the average particle diameter is smaller than 0.05 xcexcm, the amount of the porous silica particles must be increased to obtain high work efficiency, that is, slipperiness of the film, thereby impairing transparency. When the average particle diameter is 3.0 xcexcm or more, resolution may lower and the edge side of a conductor forming a circuit may not be straight but jagged. When the amount of the porous silica particles is smaller than 50 ppm, the effect of providing slipperiness is hardly developed and when the amount is 1,000 ppm or more, transparency may be impaired.
The porous silica may form coarse agglomerated particles such as a particle having an average particle diameter of 10 xcexcm or more. When the number of the coarse agglomerated particles is large, they cause a reduction in resolution and a broken film. To reduce the number of coarse agglomerated particles, a nonwoven filter made of a stainless steel thin wire having a diameter of 15 xcexcm or less and an average opening size of 10 to 30 xcexcm, preferably 13 to 28 xcexcm, more preferably 15 to 25 xcexcm is used as a filter at the time of film formation to filter a molten polymer.
Preferably, the porous silica particles or other lubricant particles are added to a reaction system (preferably as a glycol slurry) during a reaction for the production of a polyester, for example, at any time during an ester exchange reaction or polycondensation reaction in the case of the ester exchange method or at any time in the case of the direct polymerization method. Particularly preferably, the porous silica particles are added to the reaction system in the initial stage of the polycondensation reaction, for example, before the intrinsic viscosity of the polymer reaches about 0.3.
The thickness of the film of the preset invention is preferably 10 xcexcm to 25 xcexcm. It is more preferably 13 xcexcm to 23 xcexcm, more preferably 14 xcexcm to 20 xcexcm. When the thickness is larger than 25 xcexcm, resolution lowers disadvantageously. When the thickness is smaller than 10 xcexcm, strength becomes insufficient and the film is frequently broken at the time of stripping.
The haze value of the film of the present invention is 3% or less, preferably 1.5% or less, more preferably 1.0% or less.
The film of the present invention must have a transmission of ultraviolet radiation having a wavelength of 365 nm of 86% or more. When the transmission is less than 86%, the exposure and curing step of a resist layer may not complete smoothly. The UV transmission of a film having a thickness other than 16 xcexcm is evaluated based on the Lambert-Beer""s law to calculate a value based on a thickness of 16 xcexcm from the following equation:
log(Io/I)=xcex5Cd 
wherein Io is the intensity of input light, I is the intensity of transmitted light, xcex5 is an absorptivity coefficient, C is a concentration and d is the thickness of the film (xcexcm).
Preferably, the film of the present invention has a degassing rate between films of 10 to 120 mmHg/hr. When the degassing rate is within the above range, the film is wound smoothly.
The degassing rate between films is obtained by piling up twenty 8 cmxc3x975 cm film pieces cut out from the film, making a regular triangular hole having a side length of 2 mm in the centers of 19 pieces excepting a top piece from the above twenty film pieces and measuring a reduction in mmHg per unit time using a DIG-Thickness Tester (of Toyo Seiki Co., Ltd.).
The above degassing rate can be easily achieved by adding the above-described amount of inert fine particles having the above-described particle diameter to the polyester.
Preferably, the film of the present invention has a thermal shrinkage factor in a longitudinal direction measured at 150xc2x0 C. of 1.0 to 5.0%. When the thermal shrinkage factor in the longitudinal direction is smaller than 1.0%, the flatness of the film may deteriorate and the transparency of the film may degrade, thereby causing a trouble in the production process of a photoresist film and the production process of an electronic circuit. When the thermal shrinkage factor in the longitudinal direction is larger than 5.0%, the film is readily shrunk and deformed by heat and a solvent in each step.
The film of the present invention can be produced by conventionally known methods. For example, polyethylene terephthalate or copolyethylene terephthalate containing lubricant fine particles is dried, molten, extruded and solidified by quenching on a cooling drum to obtain an unstretched film, biaxially orienting the unstretched film and heat setting the film.
More specifically, this unstretched film is stretched to 3 to 5 times in a longitudinal direction at 70 to 130xc2x0 C. and then to 3 to 5 times in a transverse direction at 80 to 130xc2x0 C. and heat set at 190 to 240xc2x0 C. to obtain a biaxially oriented film. Optionally, a water-dispersible coating is applied to one side or both sides of the film during the above step, for example, after stretching in the longitudinal direction, to form a slippery, or slippery and adhesive coating film as thick as 0.01 to 0.1 xcexcm on the film. Coating is not limited but coating with a reverse roll coater is preferred.
A description is subsequently given of the laminated polyester film of the present invention. The laminated polyester film of the present invention has a lubricating layer formed on at least one side of the above biaxially oriented polyester film of the present invention as described above.
The lubricating layer may comprise (A) a copolyester having a glass transition temperature of 40 to 80xc2x0 C. and containing a dicarboxylic acid component having a group represented by xe2x80x94SO3M (M is the same equivalent as xe2x80x94SO3xe2x80x94 of a metal atom, ammonium group, quaternary organic ammonium group or quaternary organic phosphonium group) in an amount of 8 to 20 mol % based on total of all the dicarboxylic acid components, (B) an acrylic resin having a glass transition temperature of 25 to 70xc2x0 C., and (C) an inert particle lubricant.
More specifically, the lubricating layer may be formed by applying a 4% aqueous solution (coating solution) which comprises 56 parts by weight of a copolymer P of terephthalic acid, isophthalic acid, 5-Na sulfoisophthalic acid (13 mol % based on the total of all the dicarboxylic acid components), ethylene glycol and neopentylene glycol (Tg=490xc2x0 C.), 25 parts by weight of a copolymer S of methyl methacrylate, ethyl acrylate, acrylic acid, methacrylamide and N-methylolacrylamide (Tg=42xc2x0 C.), 10 parts by weight of a crosslinked acrylic resin filter (diameter of 40 nm) and 9 parts by weight of a copolymer of ethylene oxide and propylene oxide to one side of the above film with a roll coater. The thickness of the layer film is preferably 5 to 200 nm, the most preferably around 90 nm. This film thickness is equivalent to xc2xc of the wavelength of ultraviolet radiation for making a resist layer insoluble when exposed thereto and makes reflected light minimum. When the film thickness is smaller than 5 nm, slipperiness and the effect of preventing reflection are hardly obtained. When the thickness is larger than 200 nm, light transmission lowers due to multi-interference.
In the present invention, the lubricating layer can be formed on one side or both sides of the biaxially oriented polyester film of the present invention. When the lubricating layer is formed on both sides, the transmittance of radiation having a wavelength of 365 nm can be increased. However, when the lubricating layer is formed on both sides, the peel strength of the photoresist layer may become high.
Preferably, the inert particle lubricant has an average particle diameter which is smaller than twice the thickness of the lubricating layer. Examples of the inert particles are the same as those listed above.
The laminated polyester film of the present invention has an antimony metal content of preferably 15 mmol % or less, more preferably 10 mmol % or less based on the total of all the acid components.
The laminated polyester film of the present invention must have a transmission of ultraviolet radiation having a wavelength of 365 nm of 86% or more. When the UV transmission is less than 86%, the exposure and curing step of the resist layer may not complete smoothly.
The laminated polyester film of the present invention has a thermal shrinkage factor in a longitudinal direction measured after heating at 150xc2x0 C. for 30 minutes of preferably 2% or less, more preferably 1.5% or less. When the thermal shrinkage in the longitudinal direction is higher than 2%, wavy wrinkles with mountains and valleys parallel to one another in a longitudinal direction may be formed while the film is processed for DFR application, whereby the flatness of the film may be impaired.
Preferably, the number of flyspecks having a long diameter of 20 xcexcm or more contained in the laminated polyester film of the present invention is preferably 10 or less per 10 cm2. The number of flyspecks having a long diameter of 20 xcexcm or more is preferably as small as possible because they prevent light from going straight and cause a circuit defect. Since the flyspecks are generated from foreign matter. undissolved polymer or coarse particles as a nucleus, it is preferred to remove coarse particles and foreign matter by using the above-described nonwoven filter.
It should be understood that the above description of the biaxially oriented polyester film is applied to what is not described of the laminated polyester film directly or with modifications obvious to people of ordinary skill in the art.
Both of the above biaxially oriented polyester film and the laminated polyester film of the present invention are advantageously used as a base layer for the production of a dry film resist as described above.
Therefore, according to the present invention, there are provided a dry film resist comprising the biaxially oriented polyester film of the present invention, a photoresist layer and a protective film layer, and a dry film resist comprising the laminated polyester film of the present invention, a photoresist layer and a protective film layer laminated in the mentioned order, wherein when the laminated polyester film has a lubricating layer on only one side, the photoresist layer is existent on a side devoid of the lubricating layer.
The photoresist layers of the above dry film resists may be formed by applying a photoresist to a base layer in accordance with a method known per se. The protective film is provided to protect the thus formed photoresist layer until the dry film is used.
The photoresist layer in the present invention may be made from a known photosensitive resin composition but preferably it comprises (A) a binder polymer, (B) a photopolymerization initiator and (C) a photopolymerization compound having at least one polymerizable ethylenically unsaturated group in the molecule as essential ingredients, so that the layer can be developed by dilute alkali solution.
Examples of the above binder polymer (A) include an acrylic resin, styrene-based resin, epoxy-based resin, amide-based resin, amide-epoxy-based resin, alkyd-based resin and phenolic resin. An acrylic resin is preferred from the viewpoint of alkali developability. They may be used alone or in combination of two or more.
The above binder polymer may be produced by radical polymerizing a polymerizable monomer. Examples of the above polymerizable monomer include styrene, polymerizable styrene derivatives having a substituent at the xcex1-position or in the aromatic ring, such as xcex1-methylstyrene and vinyltoluene, acrylamides such as diacetone acrylamide, acrylonitrile, vinyl alcohol ethers such as vinyl-n-butyl ether, (meth)acrylic acid alkyl esters, (meth)acrylic acid tetrahydrofurfuryl esters, (meth)acrylic acid dimethyl aminoethyl esters, (meth)acrylic acid diethyl aminoethyl esters, (meth)acrylic acid glycidyl esters, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, (meth)acrylic acid, xcex1-bromo(meth)acrylic acid, xcex1-chloro(meth)acrylic acid, xcex2-furyl(meth)acrylic acid, xcex2-styryl(meth)acrylic acid, maleic acid, maleic acid anhydride, maleic acid monoesters such as monomethyl maleate, monoethyl maleate and monoisopropyl maleate, fumaric acid, cinnamic acid, xcex1-cyanocinnamic acid, itaconic acid, crotonic acid and propiolic acid.
Among the above (meth)acrylic acid alkyl esters are compounds represented by the following formula (I) and compounds obtained by substituting the alkyl groups of the compounds with a hydroxyl group, epoxy group or halogen group: 
wherein R1 is a hydrogen atom or methyl group, and R2 is an alkyl group having 1 to 12 carbon atoms. Examples of the alkyl group having 1 to 12 carbon atoms represented by R2 in the above formula (I) include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and structural isomers thereof.
The monomers represented by the above formula (I) include (meth)acrylic acid methyl esters, (meth)acrylic acid ethyl esters, (meth)acrylic acid propyl esters, (meth)acrylic acid butylesters, (meth)acrylic acid pentyl esters, (meth)acrylic acid hexyl esters, (meth)acrylic acid heptyl esters, (meth)acrylic acid octyl esters, (meth)acrylic acid 2-ethylhexyl esters, (meth)acrylic acid nonyl esters, (meth)acrylic acid decyl esters, (meth)acrylic acid undecyl esters and (meth)acrylic acid dodecyl esters. They may be used alone or in combination of two or more.
The above binder polymer (A) preferably contains a carboxyl group from the viewpoint of alkali developability and may be produced, for example, by radical polymerizing a polymerizable monomer having a carboxyl group and another polymerizable monomer. The binder polymer (A) preferably contains styrene or a styrene derivative as the polymerizable monomer from the viewpoint of flexibility.
The above binder polymers (A) may be used alone or in combination of two or more.
Examples of the above photopolymerization initiator (B) include aromatic ketones (such as benzophenone, 4,4xe2x80x2-bisdimethylaminobenzophenone (Michler""s ketone), 4,4xe2x80x2-bisdiethylaminobenzophenone, 4-methoxy-4xe2x80x2-dimethylaminobenzophenone, 2-ethylanthraquinone and phenanthrenequinone), benzoin ethers (such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether), benzoins (such as methyl benzoin and ethyl benzoin), benzyl derivatives (such as benzyl dimethyl ketal), 2,4,5-triarylimidazole dimers (such as 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4-di(p-methoxyphenyl)-5-phenylimidazole dimer, 2-(2,4-dimethoxyphenyl)-4,5-diphenylimidazole dimer and 2-(p-methylmercaptophenyl)-4,5-diphenylimidazole dimer), and acridine derivatives (such as 9-phenylacridine and 1,7-bis(9,9xe2x80x2-acridinyl)heptane). They may be used alone or in combination of two or more.
Examples of the above photopolymerization compound having at least one polymerizable ethylenically unsaturated group in the molecule (C) include compounds obtained by reacting a polyhydric alcohol with an xcex1,xcex2-unsaturated carboxylic acid, compounds obtained by reacting a 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane and a glycidyl group-containing compound with an xcex1,xcex2-unsaturated carboxylic acid, urethane monomers, nonylphenyl dioxylene (meth)acrylate, xcex3-chloro-xcex2-hydroxypropyl-xcex2xe2x80x2-(meth)acryloyloxyethyl-o-phthalate, xcex2-hydroxyethyl-xcex2xe2x80x2-(meth)acryloyloxyethyl-o-phthalate, xcex2-hydroxypropyl-xcex2xe2x80x2-(meth)acryloyloxyethyl-o-phthalate and (meth)acrylic acid alkyl esters.
The above compounds obtained by reacting a polyhydric alcohol with an xcex1,xcex2-unsaturated carboxylic acid include polyethylene glycol di(meth)acrylates having 2 to 14 ethylene groups, polypropylene glycol di(meth)acrylates having 2 to 14 propylene groups, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxy tri(meth)acrylate, trimethylolpropane diethoxy tri(meth)acrylate, trimethylolpropane triethoxy tri(meth)acrylate, trimethylolpropane tetraethoxy tri(meth)acrylate, trimethylolpropane pentaethoxy tri(meth)acrylate, tetramethylolmethane tri(meth) acrylate, tetramethylolmethane tetra(meth)acrylate, polypropylene glycol di(meth)acrylates having 2 to 14 propylene groups, dipentaerythritol penta(meth) acrylate and dipentaerythritol hexa(meth)acrylate.
Examples of the above xcex1,xcex2-unsaturated carboxylic acid include (meth)acrylic acid. Examples of the above 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl) propane include 2,2-bis(4-((meth)acryloxydiethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxytriethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypentaethoxy)phenyl)propane and 2,2-bis(4-((meth)acryloxydecaethoxy)phenyl. 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane is commercially available under the name of BPE-500 (trade name of Shin Nakamura Kagaku Kogyo Co., Ltd.).
Examples of the above glycidyl group-containing compound include trimethylolpropane triglycidyl ether tri(meth)acrylate and 2,2-bis(4-(meth)acryloxy-2-hydroxy-propyloxy)phenyl. The above urethane monomers include addition reaction products of a (meth)acryl monomer having an OH group at the xcex2-position and isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate or 1,6-hexamethylene diisocyanate, tris((meth)acryloxy tetraethylene glycol isocyanate)hexamethylene isocyanurate, EO modified urethane di(meth)acrylates and EO and PO modified urethane di(meth)acrylates. EO stands for ethylene oxide and the EO modified compounds have the block structure of an ethylene oxide group. PO stands for propylene oxide and the PO modified compounds have the block structure of a propylene oxide group.
The above (meth)acrylic acid alkyl esters include (meth)acrylic acid methyl esters, (meth)acrylic acid ethyl esters, (meth)acrylic acid butyl esters and (meth)acrylic acid 2-ethylhexyl esters. They may be used alone or in combination of two or more.
In the present invention, the amount of the component (A) is preferably 40 to 80 parts by weight based on 100 parts by weight of the total of the components (A) and (C). When the amount is smaller than 40 parts by weight, an optically cured product readily becomes brittle and if it is used as a photosensitive element, coatability may deteriorate. When the amount is larger than 80 parts by weight, sensitivity may become insufficient.
The amount of the component (B) is preferably 0.1 to 20 parts by weight based on 100 parts by weight of the total of the components (A) and (C). When the amount is smaller than 0.1 part by weight, sensitivity may become insufficient and when the amount is larger than 20 parts by weight, absorption by the surface of the composition upon exposure increases, whereby the optical curing of the interior may become unsatisfactory.
The amount of the component (C) is preferably 20 to 60 parts by weight based on 100 parts by weigh of the total of the components (A) and (C). When the amount is smaller than 20 parts by weight, sensitivity may become insufficient and when the amount is larger than 60 parts by weight, an optically cured product may become brittle.
The photosensitive resin composition in the present invention may optionally contain a dye such as Malachite Green, optically color developing agent such as tribromophenyl sulfone or leucocrystal violet, thermal color development preventing agent, plasticizer such as p-toluene sulfonamide, pigment, filler, antifoamer, flame retardant, stabilizer, adhesion providing agent, leveling agent, release promoting agent, antioxidant, perfume, imaging agent and thermal crosslinking agent in an amount of 0.01 to 20 parts by weight each based on 100 parts by weight of the total of the components (A) and (C). They may be used alone or in combination of two or more.
The photosensitive resin composition of the present invention may be dissolved in a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N-dimethyl formamide or propylene glycol monomethyl ether, or a mixed solvent thereof and applied as a solution having a solid content of 30 to 60 wt %.
The thickness of the photoresist layer which differs according to application purpose is preferably 1 to 100 xcexcm, more preferably 3 to 100 xcexcm, particularly preferably 5 to 100 xcexcm after it is dried.
The flowability of the photoresist layer is preferably 50 to 500 xcexcm, more preferably 100 to 300 xcexcm, particularly preferably 100 to 250 xcexcm from the viewpoints of followability to an adherent such as a substrate, low deformability of the photoresist layer and low edge fusibility. The flowability can be controlled to the above range by adjusting the type and amount of each component constituting the photoresist layer. The flowability is defined as T1-T2 (xcexcm) when a photoresist layer having a diameter of 20 mm and a thickness of 2 mm is used as a sample, this sample is placed on a flat substrate, a 5 kg cylindrical static load having a diameter of 50 mm is applied to the sample, and the thickness (T1 xcexcm) of the deforming photoresist layer after 10 seconds and the thickness (T2 xcexcm) of the photoresist layer after 900 seconds are measured.